Bunte salt-sulfide composition in agricultural sprays



This invention relates to agricultural spray materials. More particularly the invention relates to a novel composition that is'adapted to be mixed with water and used as an agricultural spray on thefoliage of plantsandtrees in conjunction with conventional insecticides, fungicides,

phytotoxins, animal repellents and the like to'protect these latter-materials against erosion due to w'eather conditions and thereby lengthen their --effective" life. 'This application is a continuation-in -part of our priorapplica tionserial No. 378,673, filed September 4, 1953, now abandoned.

-One of the principal'problemsthat arises inconnection with the use-of insecticides,- fungicides, etc. particularly those that are deposited'from water or organic solvent solution or dispersion is the relatively short effective life of these materials due to the fact that they'tend to be removed from the plant foliage by rain, wind-and other climatic factors. his a general object of the present invention to provide a protective coating for such materials that is firmly adherent to the foliage of plants and trees and adapted to be applied to the foliage toprevent'insecti cides, fungicides and the like from being washed therefrom by rain, thereby prolonging 'the period during which they are' effective. It is another object of the invention to provide a material that can be readily mixed with water and sprayed on to foliage to form a protective coating of the type and for the purposes described above. It may be .noted that the spray coating of the present invention can be used over a previously applied layer of thefinsecticides or can bev incorporated in the insecticide to improve its adherence to the foliage, and ineither case will protect the insecticide, fungicide, etc. from erosion. 7 It is still another object of the invention to provide a pro tective material of this type that is a substantially dry s'olid which can be readily stored-or tran'sported and which can be converted to a dispersed'form at the "point of use merely by addition to water.'

The composition of the present invention incorporates asone of itsprincipal ingredients a so-called fBunte" salt or compound analogous tofavB unte salt. As conductive to' a 'cleariunde'rstaiiding of the present invention it may be pointed out that thefBunte salts are" water soluble organic thiosulfate compounds that may be readily prepared by reacting organic monohalidesand.polyhalides ith water solubleinorganic thiosulfate s,'e.g. by refluxing 2-1-20 ,0. ,the organicghalide with; an aqueoussoluan inorganic, thiosulfate; 1 The halogen ofthe compoundis preferably attached to -an aliphatic e) carbon atom and whenthere is more than enatom; eachghalogen ,rnust be attached; to a -rbon atom; The halogenatom (or atoms) is ith a thiosulfate-radical', e.g-.;S O Na when the 'osulfate used is.sodiu-m thiosulfate.

ts broader aspects the composition of the on compris'esa substantially dry mixture of ulfate which maybe prepared in the mam ner indicated above,'and a reagent selected from the group consisting of alkali metal and alkaline earth metal monosulfides, polysulfides and hydrosulfides. It has been found that organic thiosulfate compounds react in aqueous solution very quickly with alkali metal monosulfides, polysulfides and hydrosulfides to produce organic disulfides or polysulfides. When a dry mixture of organic thiosulfate and alkaline'sulfid'e arel'ad'ded to water-there is an immediate reaction qatsroorn. temperature, e.g. 25? C., and the reactionproduct is formed as an aqueous suspension or latex of organic polymeric polysulfide. It has been found that such a suspension may be sprayed on foliage etc. which has been previously'treated with an insecticide or fungicide and has the property of protecting the in secticide or fungicide from the erosion to which it otherwise would be subjected. Moreovenit'has been found that the protective action of the polymeric polysulfide may beobtained by incorporating with" the polysulfide suspension a solution or suspension of a conventional insecticide or fungicide and using the composite product thus obtained as a material' yvhich may be applied in a single spraying operationI- iAls'o the dry mixture of organic thiosulfate and alkalinetsulfide can be premixed with a suitable insecticide or fungicide, and then added to water at the point of use to provide a'spray solution or suspension containing both the insecticide or fungicide and the material to cause it to adhereto' the foliage "While we do 'not wish to: be bound byany particular theory of operationof the present invention; it is-our belief that thereaction between the organic thiosulfate and alkaline sulfide involves a scission of the S -SO bond in the organic thiosulfate with the rejoining of the fragments to give the products indicatedbelow. The reaction may be summed up'in the following equations wherein R represents the organic radical of theorganic thiosulfate, the nature of which; 'is' described more fully hereafter, and various} different sulfide reagents are to illustrate different species of the reaction.

used

As indicatedabove, the foregoing reactions proceed very rapidly at room. temperature. Hence whateverthe mechanism-of these reactions may be it seems clear' that they are quite different from the known reaction between an organic halide or' material with labile groups and an alkali metalpolysulfide. In therlatter typeof'reaction,"

the bond' is broken where X ishalogen or'other. labile'group and this; reaction ,is known to proceed quite slowly atroorn, temperaturef Hence it seems clear that the reaction between the organic thiosulfate. and the alkali metal ,sulfideaccording to the above ganic halides and alkali metal polysulfides. t. The organic radical of the:organic thiosulfate is -desirably either'an aliphatic hydrocarbon or gdxahy'droca'r proportion of the organic thiosulfate be bi-functional, i.e.

that it have the radical S Q Na attached toreachoftwo different methylene carbon-atoms. Exampleso tional organic thiosulfates useful inthepresent U tion are given in T bile I below wherein I indicat ll sulfate radicaI QOaNa." l

equations. isfunda 7 l mentally ditferent from the known reaction between tor-1 3 TABLE 'I THI'OSULFATESOF OXAHYDROCARBONS A. Thiosulfates of ethers T011140 O CzH4T CHCH TC HAQ O CZHAT B. Thiosulfates of formals CH2O CHzOClHtT CHOCHaOCzHtT CHaO CHzO CSHAT TCH: CHQT cnoornoon TCH: CHaT TnrosoL Arns or HYDROCARBONS TC l-l T n from 3 to about 10.

It has been found that mixtures of the foregoing thiosulfates can be used as well as individual compounds. As indicated above, it .is preferable that bi-functional thiosulfates be used and where mixtures of thiosulfates are used at least a major proportion of the organic thiosulfate should be bi-functional. On the other hand there are various instances where a minor proportion of a mono-functional thiosulfate, or a thiosulfate containing more than two thiosulfate groups can be used with advantage. For example, it has been found that a mixture comprising 80 mol percent of bi functiOnaI thiosulfate and mol percent of a mono-functional thiosulfate when mixed with an alkali metal sulfide, polysulfide, or sulfhydrate and used according to the present invention gives a protective coating having exceptionally good adhesion. More generally an increase in the amount of monofunc tional compound in a mixture of monoand bifunctional compounds increases the stickiness of the resulting coating. However it usually is not desirable to use more than about of the mono-functional compound since large proportions of the mono-functional compound produce a liquid product. The monofunctional and poly-functional organic thiosulfates can he prepared by methods analogous to those described above.

-In addition to the organic thiosulfate and alkali metal sulfide the composition of the present invention may include a dispersing agent to promote dispersion of the polysulfide polymer particles when the composition is mixed with water and to improve the stability of the resulting suspension. The dispersing agent may be incorporated in the dry mixture and when used is preferably employed in an amount of from 0.05% to 5% by weight of the mixture.

Dispersing agents in general may be used and examples of useful dispersing agents are given in the following table.

. TABLE II 1. Alkyl arylsulfonates, e.g. butyl naphthalene sulfonate, '2.'Alkyl sulfates,-e.g. lauryl sulfate 3. Polymerized alkyl naphthalene 'sulfonates grams (0.01 mol) of the organic thiosulfate was blend Sorbitan monolaurate The above list includes both ionic and non-ionic types of materials. have to be incorporatedin an inert carrier such as bentonite before being admixed with the organic thiosulfate and alkali metal sulfide. I

As previously indicated the composition described above can, if desired, be mixed with a conventional insecticide, fungicide, phytotoxic substance or animal repellent and then added to water to form a spray material which will deposit on the foliage both the insecticide,

0 etc. and the sticky material which prevents erosion of the insecticide. Typicalsubstances of this type are dichlorodiphenyltrichloroethane (DDT), the gamma isomer of hexachlorcyclohexane (lindane), 2-(paratertiarybutylphenoxy) isopropyl-Z-chloroethyl sulfite (aramite), ferricdimethyldithiocarbarnate (ferbam), the isopropyl ester of 2,4-dichlorophenoxyacetic acid (2,4D) and sulphur. In cases where the protective erosion-preventing material is mixed with the insecticide or the like in dry form, it is desirably present to the extent of l to 30% by weight of the mixture. The preferred composition is of the order of by weight of the insecticide and 10% of the material that forms the adherent coating. As pointed out above, the insecticide or fungicide is not an essential component of the composition, since the composition may be used to apply a protective coating after the insecticide has been previously applied. It may be noted that when the present composition is used with out a conventional insecticide it has inherently a moderate fungicidal action, roughly comparable to that of sulfur.

In order to point out more fully the nature of the present invention, the following specific examples are given of illustrative compositions according to the invention and methods by which they may be made.

EXAMPLE 1 A quantity of the product of Example 1 containing 5.4

with 2.4 grams of commercial 70% calcium polys (lime-sulfur) containing 0.01 mol of the polysulfid blend was pulverized to pass through a -mes This mixture was stable for a number of week temperature if kept dry. On addition of 3.5 gr blended powder to 35 cc. water, a coarse lat alkylene polysulfide polymer was formed.

EXAMPLE 3 7.8 grams of the blendedwdithios pqlysullideohtained in Example 2. eref Coconut fatty acid diamide of diethanolamine 5 It also includes certain liquids which may l gsam of dry polymeric alkyl aryl sulfonate.

than in the case of Example'2.. Similar results are obtained by use of Nacconol NRSF an alkyl aryl-sulfonate) and other similar surface-active agents. 7 r

EXAMPLE 4 5.4 grams (0.01 mol) of the same, dithiosulfate as obtained in Example 1 was blended with 4.8 grams (0.02 mol) of commercial 70% calciumpolysulfide. Addition of 3.5 grams of this blend to 35 cc. .water' gave a coarse latex suspended in a liquid which was orange in color, which indicated the excess of polysulfide in solution.

5.4 grams (0.01 mol) of dithiosulfate'derived in Example 1 from dichlordiethyl ether, was blended with 1.2 grams (0.005 mol) of commercial 70%. calcium polysulfide. The resulting mixture, was pulverized topass through'a 100-mesh screen. Addition of,3.5 grams of this blend to 35 cc. water gave a latex which coarsenedon standing and was therefore not particularly stable. In thisfexample the supernatant liquid was colorless.

. EXAMPLE 6 o a a 5 .4 grams (0.01 mol) of the dithiosulfate from dichlor- From the foregoing description and examplesg'it shouldbe apparent that the present invention provides a compo sition capable of achieving the several objectives set-forth at the beginning of the present specification. The dry mixture of organic thiosulfate and alkaline sulfide, either with or without the dispersing agent and insecticide, etc.,' is quite stable and remains stable as long as its dry con dition is maintained. (The word dry as used herein means the absence of free water and does not exclude, the presence of combined water such as water of crystallization.) The composition is readily miscible with water' at the point of use -to form a fine dispersion that can be sprayed on the foliage and when so sprayed deposits-a rubbery protective layer that effectively prevents either a previously applied insecticide or a component insecticide from being washed from. the foliage by rain or eroded by wind, dust and the like.

,Although, the .series of equations given'above indicates a that one mol of sulfide reagent isrequired for each mol of organic dithiosulfate, it has been found that less than advantage in some cases; The use of a molar ratio of diethyl ether was blended with 1.3 grams of commercial sodium monosulfide nonahydrate' and the mixture'finely' Proceed as in Example l using 99 grams (1.0 mol) of ethylene dichloride in place of dichlordiethyl ether.

Evaporation of the reaction liquid obtained after refluxing for several hours at atemperature of 95-120 C.

70% calcium polysulfide, and'0.25 gram'of a polymeric alkyl aryl sulfonate. On addition of the mixture to water there was obtained a finely dispersed latex.

EXAMPLE 9 129 gram (0.90 mol) dichlordiethyl ether and 919 grams (0.10 mol) ethylene dichloride were refluxed in about 0.5 is illustrated in ExamplesS and 6 above. In

general it is preferable that at least0.5 mol of sulfide reagent be used for each two *S O Na groups of the organic thiosulfate. T

It is of course to be understood that the foregoing examples are illustrative only and, that numerous changes can bemade in the specific illustrative compositions disclosed withoutgdeparting from the spirit of the invention as defined in the-appended claims. -We'claim: 1.;A solid, substantially dry composition adapted to be mixed with water to forml'a water dispersion of poly- A sulfide polymer, said composition comprising at least one compound having the general formula R(S O Na),. wherein R is selected from the group consisting 'of oxahydrocarbon radicals and aliphatic hydrocarbon radicals having up to ten carbon atoms, and x is a positive integer from 1 to 4, at least a majorproportion of the molecules of said compounds having at least two S O Na.

radicals attached to different carbon atoms thereof, and

'a reagent selected from the group consisting of alkaline monosulfides, polysulfides and sulfhydrates.

' prising a mixture of compounds having the general for- Y mula R(S O Na) wherein R is selected from the group thiosulfates derived from the two organic halides together with sodium chloride resulting from the reaction, and unreacted sodium thiosulfate.

EXAMPLE I 10 i 5.4 grams (0.1 mol) of the dry mixture obtained persed latex.

X EXAMPLE 11 5.4 grains (0.01 mol) of the dry mixture as obtained in Example 9 was treated with 2.9 grams (0.03 mol) technical grade dry sodium hydrosulfide and 0.5 gram of a dryi polymeric alkyl aryl sulfonate. Addition to this blend, to water gave a dispersion of polymeric poly sulfide polymer.

consisting of oxahydrocarbon radicals and aliphatic hydrocarbon radicals having up to ten carbon atoms, and x is positive integer from 1 to 4, a major proportion of the molecules of said mixture having two S 0 Na radicals attached to diiferent carbon'atoms thereof and a minor proportion having only one S O Na radical attached to a carbon atom thereof, and a reagent selected from the group consisting of alkaline monosulfides', polysulfides and sulfhydrates.

3. A composition according to claim 1 and wherein approximately of the molecules of said compounds have two S O Na radicals attached thereto and approximately 20% of the molecules of said mixture have only one S O Na radical attached thereto.

.4. A solid, substantially dry composition adapted to composition comprising a compound selected from the group consisting of sodium thiosulfates of aliphatic hydrocarbons having up to ten carbon atoms and oxahy-- drocarbons, said compound having the radical S,O,Na

attached to each of two different carbon atoms thereof,

oms, and x is a positive integer from 1 to 4, at least a g major proportion of the molecules of said compounds having at least two S O Na radicals attached to different carbon atoms thereof, a reagent selected from the group consisting of alkaline monosulfides, polysulfides and sulfhydrates, and from 0.05 to by weight of a dispersing agentbased ,on the dry weight of said composition.

6. A solid substantially dry composition adapted to be mixed with Water and used as an agricultural spray having good adhesion to foliage, said composition being essentially composed of from 70 to 99% by Weight of an insecticide and from 1 to 30% of a material adapted to inhibit removal of the insecticide from plant foliage, having the general formula R(S O Na),, wherein R is selected from the gorup consisting of oxahydrocarbon radicals and aliphatichydrocarbon radicals having up to ten carbon atoms, and x is a positive integer from 1 to ,4, at least a major proportion of the molecules of said compounds having at least two S -O Na radicals attached to different carbon atoms thereof, and a reagent selected from the group consisting of alkaline monosulfides, polysulfides and sulfhydrates.

7. A solid substantially dry composition adapted to be mixed wtih water and used as an agricultural spray having good adhesion to foilage, said composition comprising a compound selected from the group consisting of sodium thiosulfates of aliphatic hydrocarbons having upto ten carbon atoms and oxahydrocarbons, said compound having the radical S O Na attached to each of two different carbon atoms thereof, a reagent selected from the group consisting of alkaline monosulfides, poly sulfides and sulfhydrates, said reagent being present to the extent of at least 0.5 mol thereof for each two S O Na groups, and from 0.0055% by weight of a dispersing agent and from 70% to 99% by weight of an insecticide, both based on the dry weight of said composition.

'8- A l d su tantia vs y t-sqmpqs i a t-adantedtto b m xe w h a er a d sed as an a icu l @11 2 having g od adhes e to fol e a d nmno ition be n e e ia y mpos d o b u y Weight o a sub nce s le ted o he g o p co ist ng o in tic des, fungicides, phytotoxins and animal repellents and abopt 10% of a material adapted to inhibit removal of said substance from plant foliage, said material comprising at least one compound having the general formula wherein R is selected from the group consisting of oxahydrocarbon radicals and aliphatic hydrocarbon radi cals having up to ten carbon atoms, and xi is a positive integer from 1 to 4, at least a major proportion of the molecules of said compounds having at least two S O Na radicals attached to different carbon atoms thereof and a reagent selected from the group consisting of alkaline monosulfides, polysulfides and sulfhydrates.

9. A solid, substantially dry composition adapted to be mixed with water at normal atmospheric temperatures to form a water dispersion of polysulfide polymer, said composition comprising at least'one compound having the general formula R S O Na),, wherein R is selected from the group consisting of oxahydrocarbon radi cals and aliphatic hydrocarbon radicals having up to ten carbon atoms, and x is a positive integer from 1 to 4, at least a major proportion of the molecules of said compounds having at least two S O Na radicals attached to different carbon atoms thereof, and a reagent selected from the group consisting of alkaline monosulfides, poly, sulfides and sulfyhydrates said reagent being present to the extent of at least 0.5 mol thereof foreach two S Q Na groups.

References Cited in the file of this patent UNITED STATES PATENTS Patent should 'readas corrected below.

a "gorup" read group v UNITED STATES PATENT OFFICE I CERTIFICATE OF CORRECTION g Patent No. 2,925,362

Edward M. Fettes et .31;

It is hereby certified that error appears in the printed specification February 16, 1960 of the above numbered patent requiring correction and that the said Letters Column 7 line 22, after "foliage," insert -e said material comprising at least one'compound line 24, for

Signed and sealed this 11th day of October 1960.

(SEAL) Attest: Kim H. AXLINE Y 2. ROBERT c. WATSON Attesting Officer Commissioner of Patents 

1. A SOLID, SUBSTANTIALLY DRY COMPOSITION ADAPTED TO BE MIXED WITH WATER TO FORM A WATER DISPERSION OF POLYSULFIDE POLYMER, SAID COMPOSITION COMPRISING AT LEAST ONE COMPOUND HAVING THE GENERAL FORMULA R(S2O3NA)X WHEREIN "R" IS SELECTED FROM THE GROUP CONSISTING OF OXAHYDROCARBON RADICALS AND ALIPHATIC HYDROCARBON RADICALS HAVING UP TO TEN CARBON ATOMS, AND "X" IS A POSITIVE INTEGER FROM 1 TO 4, AT LEAST A MAJOR PROPORTION OF THE MOLECULES OF SAID COMPOUNDS HAVING AT LEAST TOW S2O3NA RADICLAS ATTACHED TO DIFFERENT CARBON ATOMS THEREON, AND A REAGENT SELECTED FROM THE GROUP CONSISTING OF ALKALINE MONOSULFIDES, POLYSULFIDES AND SULFHYDRATES. 